WO2004065448A1 - Hydrophobic propellant gas mixtures for producing insulating foams - Google Patents

Hydrophobic propellant gas mixtures for producing insulating foams Download PDF

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Publication number
WO2004065448A1
WO2004065448A1 PCT/EP2003/014765 EP0314765W WO2004065448A1 WO 2004065448 A1 WO2004065448 A1 WO 2004065448A1 EP 0314765 W EP0314765 W EP 0314765W WO 2004065448 A1 WO2004065448 A1 WO 2004065448A1
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WO
WIPO (PCT)
Prior art keywords
prepolymer
propellant gas
gas component
component
composition according
Prior art date
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PCT/EP2003/014765
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German (de)
French (fr)
Inventor
Heinrich Sommer
Barbara Poggenklas
Original Assignee
Rathor Ag
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Publication date
Application filed by Rathor Ag filed Critical Rathor Ag
Priority to US10/543,038 priority Critical patent/US20060186374A1/en
Priority to AT03815373T priority patent/ATE481433T1/en
Priority to EP03815373A priority patent/EP1585778B1/en
Priority to DE50313106T priority patent/DE50313106D1/en
Priority to AU2003296712A priority patent/AU2003296712A1/en
Publication of WO2004065448A1 publication Critical patent/WO2004065448A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

Definitions

  • the invention relates to a prepolymer composition for the production of insulating foams from pressure vessels, with a prepolymer component which has a prepolymer with silane groups for crosslinking the prepolymer with a second component, as well as conventional additives, and a propellant gas component which is liquid under the pressure prevailing in the pressure vessel and is at least partially dissolved in the prepolymer components, and the use of certain propellant gas mixtures for the production of insulating foams from prepolymers containing polar reactive groups.
  • Insulating foams for foaming cavities are often produced as local foams from pressure cans using polyurethane prepolymer blends.
  • the main areas of application are construction, but also technical products in which cavities have to be filled in to avoid condensation nests.
  • Prepolymers for producing polyurethane insulation foams have polyisocyanate groups capable of crosslinking, which react with a polyol component or water to form the actual polymer.
  • the foam structure is generated by CO 2 generated in the reactions with water and / or propellant present in the prepolymer blend.
  • isocyanate groups capable of crosslinking
  • Prepolymer compositions are currently predominant Related propellant gas mixtures, which contain butanes, propane, dimethyl ether, optionally together with fluorocarbons.
  • A1 prepolymer blends are also known which, when attached to a polyurethane structure, have terminal silane groups as reactive groups which are suitable for reacting with water as the second component. This reaction releases an alkanol, usually methanol.
  • these silane-terminated foams have the advantage that the prepolymers used do not have toxic isocyanate functions.
  • the methanol released in the silane-terminated foams is considered to be less problematic, also because of the relatively small amounts and rapid evaporation.
  • the silane-terminated prepolymers have the potential to replace the conventional isocyanate-terminated prepolymers.
  • foams with a very fine cell structure are obtained, provided that these foams are applied to a flat work surface.
  • foaming joints as is the case in practice with the foaming of door and window frames, it is found that the foam that has oozed out of the joint has a good cell structure, but the foam structure within the joint has defects and cracks, which at least question the insulating effect of the foam, but sometimes also its assembly properties. In extreme cases, the foam collapses almost completely.
  • the object of the invention is to provide a prepolymer composition, in particular for the production of insulating foams from silane-terminated prepolymers, which are improved with regard to foam stability and crack behavior.
  • prepolymer compositions of the type mentioned at the outset give stable and good foams when they are equipped with a propellant gas component which has a log Po / w value of 1 1.70, where Po / w is the distribution coefficient of the propellant gas component in octanol Is water.
  • the value log Po / w 1 1.90 is preferred.
  • silane groups are preferably terminal silane groups on a polyurethane structure known per se and in particular methoxy and ethoxysilane groups.
  • the functionality of the prepolymer is> 2. Preference is given to trimethoxysilane and methyldimethoxysilane functions.
  • the distribution coefficient Po / w represents, here in logarithmic representation, the distribution of a substance in a non-polar (octanol) and a polar (water) solvent.
  • the decimal logarithm of the Po / w value of a blowing agent is used.
  • the mean of the log Po / w values of the individual propellant gases of the mixture, weighted with the amount of propellant gas in grams, is calculated and taken as the limiting criterion. It has been shown that the weighted mean of the logarithmic values represents a sufficiently precise approximation.
  • the non-polarity of the propellant gas component is associated with the polarity of the prepolymer component and / or the agents released from the reactive groups, for example methanol or ethanol from prepolymers terminated with methoxy or ethoxysilane.
  • the design rules according to the invention apply to both one-component and two-component foams. They are also applicable to foams which only partially react with a second component released within a pressure vessel and, moreover, with water contained in the atmosphere, so-called 1.5-component foams.
  • the stabilizing effect according to the invention of the non-polar or hydrophobic setting of the propellant gas component is based on the fact that the propellant gases are better retained within the cells formed after foaming because they are poor in the polar, which may also be additionally enriched with methanol or ethanol Loosen cell membranes. By delaying the dissolving effect, the prepolymer has time to cross-link, the alcohol to evaporate and the foam to cure.
  • the related prepolymer components according to the invention are those as are known from the prior art. These can be, for example, isocyanate-terminated, but also silane-terminated, as is known, for example, from WO 00/04069 A1. Such silane terminated
  • Prepolymers are based on a conventional polyurethane backbone consisting of an aromatic or aliphatic polyisocyanate and a polyol, the isocyanate groups of which have been functionalized by reaction with a silane compound reactive therewith.
  • Suitable silane groups are, for example
  • Aminomethoxysilanes in particular N-phenylaminomethyltrimethoxysilane and
  • Prepolymers can be found in WO 00/04069 A1 and WO 02/66532 A1, WO 02/68491 A1, WO 02/70586 A1 and WO 02/77072 A1, the
  • the minimum value to be observed for the log Po / w which according to the invention is ⁇ 1.70, depends to a certain extent on the polarity of the prepolymer or the polarity of the product of the crosslinking reaction released from the prepolymer and its amount.
  • a limit value of log Po / w ⁇ 1.90 is in any case applicable for dimethoxymethylsilane-terminated prepolymers which release only two molecules of methanol per silane unit when crosslinked. When using trimethoxysilane-terminated prepolymers, three molecules of methanol are released per silane group, the last of which in a delayed crosslinking reaction after the first two.
  • propellant components used are non-polar and hydrophobic.
  • Particularly suitable propellants are hydrocarbons with up to 5 carbon atoms, both saturated and unsaturated, as well as fluorocarbons, and especially i-butane, n-butane, propane, R227ea (1, 1, 1, 2,3,3,3- Heptafluoropropane), R365mfc (1, 1, 1, 3,3-pentafluorobutane), R245fa (1, 1, 1, 3,3-pentafluoropropane), R134a (1, 1, 1, 2-tetrafluoroethane), R152a (1, 1- difluoroethane) and, to a limited extent, DME (dimethyl ether).
  • propellant gases can be used alone, in any mixture as well as in a mixture with other propellant-capable compounds.
  • the propellant gas component should have a boiling point of ⁇ 40 ° C and in particular ⁇ 20 ° C, depending on the area of application and conditions of use.
  • the viscosity can be adjusted, for example, with conventional phosphates, which also have a flame-retardant effect, for example with triethyl phosphate.
  • vinyltrimethoxysilane can also be used in a known manner, which has a positive influence on the solubility of the propellant gas component in the prepolymer component.
  • Vinyltrimethoxysilane also serves as an adhesion promoter for the product, but releases additional amounts of methanol when reacting with air humidity.
  • the polarity of the prepolymer component, its releasable methanol content, its absorption capacity / solvent capacity for the propellant gas component and the polarity of the foam formed can be influenced and adjusted by the vinyltmmethoxysilane content of the prepolymer composition.
  • Dimethyl ether can be used to fine-tune the polarity of the propellant gas component because it has an extremely low log Po / w value. In general, however, dimethyl ether is not suitable for achieving higher log Po / w values.
  • the propellant gas component generally makes up 20 to 40% by volume of the prepolymer composition according to the invention, in particular approximately 25 to 35% by volume.
  • the propellant gas component preferably consists of at least 2/3 of non-polar components, in particular at least 5/6. Components with a log P 0 / w value of> 1.35 are regarded as non-polar components.
  • prepolymer compositions according to the invention contain customary additives, such as catalysts from the preparation and crosslinking reactions, stabilizers, viscosity and rheology regulators, cell regulators, plasticizers, flame retardants and the like.
  • the NCO content of the finished prepolymer is theoretical 11.2% and is determined titrimetrically by the reaction of prepolymer with dibutylamine in toluene solution and subsequent back titration with HCl solution. After a constant NCO content has been reached, vinyltrimethoxysilane is added and the mixture is stirred vigorously for a further 5 min. Composition for the recipes:
  • the prepolymer obtained in this way is weighed directly into the aerosol can with the additives (foam stabilizer, amine catalyst), vinyltrimethoxysilane as diluent and adhesion promoter. Then the slightly over-stoichiometric addition of the aminosilane takes place, the closure with a conventional valve and immediate injection of the propellant gas. When the addition is complete, shake vigorously. The internal temperature rises by 20 to 30 ° C within 30 s. The cans are ready for use after overnight storage at room temperature.
  • the additives foam stabilizer, amine catalyst
  • vinyltrimethoxysilane as diluent and adhesion promoter.
  • Prepolymer 1 reaction product of PU prepolymer with
  • Prepolymer 2 reaction product of PU prepolymer with
  • the prepolymer compositions listed in the table below were prepared with the propellant components indicated and were foamed from a conventional pressure can.
  • the related stabilizer is a foam stabilizer from Goldschmidt AG in Essen, the catalyst ZF-20 bis (2-dimethylaminoethyl) ether from Huntsman.
  • two particle boards with the dimensions 14 x 14 x 1.9 cm were immersed in water for 20 s. Then the plates were set up vertically for 100 s in order to allow the water to run off and to avoid standing moisture.
  • a horizontal joint measuring 14 x 9.5 x 2.5 cm was shown with joint spacers (rods made of polyethylene).
  • the joint was weighted with a weight of 12.5 kg and completely foamed. After a day, the swollen foam was cut off and the foam quality in the joint was assessed. For this, the joint was cut lengthways.
  • the values 1 (homogeneously hardened foam joint), 2 (crack formation in the foam joint) and 3 (complete collapse in the joint) were assigned for evaluation. The results are also shown in the table below.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a prepolymer composition, particularly for producing insulating foams coming out of pressure packs. The prepolymer composition comprises a prepolymer component, which contains a prepolymer with silane groups for cross-linking the prepolymer with a second component and contains customary additives, and comprises a propellant gas component, which is liquid under the pressure prevailing in the pressure pack and which is at least partially dissolved in the prepolymer component. The propellant gas component has a value log PO/W of ≥ 1.90, whereby PO/W represents the distribution coefficient of the propellant gas component in octanol/water. The invention also relates to the use of a propellant gas mixture with a value log PO/W of ≥ 1.90 for producing insulating foams from prepolymers containing polar reactive groups in pressure packs.

Description

Hydrophobe Treibαasmischunαen für die Erzeugung von Dämmschäumen Hydrophobic blowing α mixtures for the production of insulating foams
Die Erfindung betrifft eine Prepolymerzusammensetzung für die Erzeugung von Dämmschäumen aus Druckbehältem, mit einer Prepolymerkomponenten, die ein Prepolymer mit Silan-Gruppen zur Vernetzung des Prepolymers mit einer zweiten Komponenten aufweist sowie übliche Zusätze, und einer Treibgaskomponenten, die unter dem im Druckbehälter herrschenden Druck flüssig ist und zumindest teilweise in der Prepolymerkomponenten gelöst vorliegt, sowie die Verwendung von bestimmten Treibgasmischungen für die Erzeugung von Dämmschäumen aus polare reaktive Gruppen aufweisenden Prepolymeren.The invention relates to a prepolymer composition for the production of insulating foams from pressure vessels, with a prepolymer component which has a prepolymer with silane groups for crosslinking the prepolymer with a second component, as well as conventional additives, and a propellant gas component which is liquid under the pressure prevailing in the pressure vessel and is at least partially dissolved in the prepolymer components, and the use of certain propellant gas mixtures for the production of insulating foams from prepolymers containing polar reactive groups.
Dämmschäume zum Ausschäumen von Hohlräumen werden vielfach als Ortschäume aus Druckdosen unter Verwendung von Polyurethan- Prepolymerabmischungen erzeugt. Hauptsächliche Anwendungsgebiete sind das Bauwesen, aber auch technische Produkte, bei denen Hohlräume zur Vermeidung von Schwitzwassernestern verfüllt werden müssen.Insulating foams for foaming cavities are often produced as local foams from pressure cans using polyurethane prepolymer blends. The main areas of application are construction, but also technical products in which cavities have to be filled in to avoid condensation nests.
Prepolymere zur Erzeugung von Polyurethan-Dämmschäumen besitzen zur Vernetzung befähigte Polyisocyanat-Gruppen, die mit einer Polyolkomponente oder Wasser unter Bildung des eigentlichen Polymeren reagieren. Die Schaumstruktur wird durch bei der Reaktionen mit Wasser erzeugtes CO2 und/oder in der Prepolymerabmischung vorhandenes Treibgas erzeugt. Zur Verschäumung von Isocyanat-Gruppen enthaltendenPrepolymers for producing polyurethane insulation foams have polyisocyanate groups capable of crosslinking, which react with a polyol component or water to form the actual polymer. The foam structure is generated by CO 2 generated in the reactions with water and / or propellant present in the prepolymer blend. For foaming isocyanate groups
Prepolymerzusammensetzungen werden derzeit überwiegend Treibgasmischungen verwandt, die Butane, Propan, Dimethylether, gegebenenfalls zusammen mit Flurkohlenstoffen enthalten.Prepolymer compositions are currently predominant Related propellant gas mixtures, which contain butanes, propane, dimethyl ether, optionally together with fluorocarbons.
Aus der WO 00/04069 A1 sind weiterhin Prepolymerabmischungen bekannt, die angehängt an ein Polyurethan-Gerüst, terminale Silan-Gruppen als reaktive Gruppen aufweisen, die geeignet sind, mit Wasser als zweiter Komponente zu reagieren. Bei dieser Reaktion wird ein Alkanol, üblicherweise Methanol, freigesetzt.From WO 00/04069 A1 prepolymer blends are also known which, when attached to a polyurethane structure, have terminal silane groups as reactive groups which are suitable for reacting with water as the second component. This reaction releases an alkanol, usually methanol.
Grundsätzlich haben diese silanterminierten Schäume den Vorteil, daß die dazu verwandten Prepolymere nicht über toxische Isocyanatfunktionen verfügen. Das bei den silanterminierten Schäumen freigesetzte Methanol wird, auch wegen der relativ geringen Mengen und schnellen Verdunstung, als wenig problematisch angesehen. Insoweit haben die silanterminierten Prepolymere das Potential, die herkömmlichen isocyanatterminierten Prepolymere zu ersetzen.Basically, these silane-terminated foams have the advantage that the prepolymers used do not have toxic isocyanate functions. The methanol released in the silane-terminated foams is considered to be less problematic, also because of the relatively small amounts and rapid evaporation. In this respect, the silane-terminated prepolymers have the potential to replace the conventional isocyanate-terminated prepolymers.
Bei der Verschäumung von silanterminierten Prepolymeren mit üblichen Treibgasmischungen werden jeweils Schäume mit sehr feiner Zellstruktur erhalten, soweit diese Schäume auf einer ebenen Arbeitsfläche ausgebracht werden. Beim Ausschäumen von Fugen, wie das in der Praxis bei der Einschäumung von Tür- und Fensterzargen der Fall ist, stellt man aber fest, daß der aus der Fuge herausgequollene Schaum eine gute Zellstruktur aufweist, die Schaumstruktur innerhalb der Fuge jedoch Fehlstellen und Risse aufweist, die zumindest die Dämmwirkung des Schaums, teilweise jedoch auch seine Montageeigenschaften in Frage stellen. In extremen Fällen wird der praktisch vollständige Kollaps des Schaums festgestellt.When foaming silane-terminated prepolymers with conventional propellant mixtures, foams with a very fine cell structure are obtained, provided that these foams are applied to a flat work surface. When foaming joints, as is the case in practice with the foaming of door and window frames, it is found that the foam that has oozed out of the joint has a good cell structure, but the foam structure within the joint has defects and cracks, which at least question the insulating effect of the foam, but sometimes also its assembly properties. In extreme cases, the foam collapses almost completely.
Untersuchungen haben ergeben, daß diese Probleme mit Schäumen aus silanterminierten Prepolymeren mit der Freisetzung von Methanol zusammenhängen. Das Methanol weicht beim Austritt aus dem Schaum die Zellstrukturen auf und macht sie aufnahmefähig für das Treibgas. Der Verlust des Treibgases vor der endgültigen Aushärtung bringt den Schaum zum Kollaps. Rißfreie Schaumstrukturen mit guter Zellstruktur können aus silanterminierten Prepolymeren jedenfalls mit herkömmlichen Treibgasmischungen, wie sie aus der Verschäumung von Isocyanat-Gruppen enthaltenden Prepolymeren bekannt sind, etwa Butan-, Propan-, Dimethylether-, Fluorkohlenwasserstoffmischungen, nicht erzielt werden.Studies have shown that these problems with foams made from silane-terminated prepolymers are related to the release of methanol. As it emerges from the foam, the methanol softens the cell structures and makes them receptive to the propellant gas. The loss of the propellant gas before the final curing causes the foam to collapse. Crack-free foam structures with a good cell structure can in any case be made from silane-terminated prepolymers with conventional propellant mixtures, such as those resulting from the foaming of isocyanate groups containing prepolymers are known, such as butane, propane, dimethyl ether, fluorocarbon mixtures, can not be achieved.
Dementsprechend liegt der Erfindung die Aufgabe zugrunde, eine Prepolymerzusammensetzung insbesondere für die Erzeugung von Dämmschäumen aus silanterminierten Prepolymeren bereitzustellen, die hinsichtlich der Schaumstabilität und des Rißverhaltens verbessert sind.Accordingly, the object of the invention is to provide a prepolymer composition, in particular for the production of insulating foams from silane-terminated prepolymers, which are improved with regard to foam stability and crack behavior.
Es wurde überraschend gefunden, daß Prepolymerzusammensetzungen der eingangs genannten Art dann stabile und gute Schäume ergeben, wenn sie mit einer Treibgaskomponente ausgerüstet werden, die einen Wert log Po/w von ≥ 1 ,70 aufweist, wobei Po/w der Verteilungskoeffizient der Treibgaskomponente in Oktanol Wasser ist. Bevorzugt beträgt der Wert log Po/w ≥ 1 ,90.It has surprisingly been found that prepolymer compositions of the type mentioned at the outset give stable and good foams when they are equipped with a propellant gas component which has a log Po / w value of 1 1.70, where Po / w is the distribution coefficient of the propellant gas component in octanol Is water. The value log Po / w 1 1.90 is preferred.
Silan-Gruppen im Sinne der Erfindung sind vorzugsweise terminale Silan- Gruppen an einem an und für sich bekannten Polyurethangerüst und insbesondere Methoxy- und Ethoxysilan-Gruppen. Die Funktionalität des Prepolymers beträgt > 2. Bevorzugt sind Trimethoxysilan- und Methyldimethoxysilanfunktionen.For the purposes of the invention, silane groups are preferably terminal silane groups on a polyurethane structure known per se and in particular methoxy and ethoxysilane groups. The functionality of the prepolymer is> 2. Preference is given to trimethoxysilane and methyldimethoxysilane functions.
Die Polarität bzw. Hydrophobie der Treibgaskomponente scheint einen entscheidenden Einfluß auf die Schaumstabilität auszuüben. Der Verteilungskoeffizient Po/w gibt, hier in logarithmischer Darstellung, die Verteilung eines Stoffes in einem unpolaren (Oktanol) und einem polaren (Wasser) Lösungsmittel wieder. Je größer der Wert von log Po/w ist, desto geringer ist die Polarität des gemessenen Stoffes und desto größer ist seine Affinität für unpolare Kohlenwasserstoffe und seine Hydrophobie.The polarity or hydrophobicity of the propellant gas component seems to have a decisive influence on the foam stability. The distribution coefficient Po / w represents, here in logarithmic representation, the distribution of a substance in a non-polar (octanol) and a polar (water) solvent. The greater the value of log Po / w, the lower the polarity of the measured substance and the greater its affinity for non-polar hydrocarbons and its hydrophobicity.
Erfindungsgemäß wird der dekadische Logarithmus des Po/w-Wertes eines Treibmittels herangezogen. Bei Treibgasmischungen, wie sie üblicherweise verwandt werden, wird das mit der Treibgasmenge in Gramm gewichtete Mittel der log Po/w-Werte der einzelnen Treibgase der Mischung berechnet und als Grenzkriterium genommen. Es hat sich gezeigt, daß das gewichtete Mittel der logarithmischen Werte eine hinreichend genaue Näherung darstellt. Im Ergebnis wurde gefunden, daß bei den silangruppenhaltigen Prepolymeren die Unpolarität der Treibgaskomponente einhergeht mit der Polarität der Prepolymerkomponente und/oder der aus den reaktiven Gruppen freigesetzten Agenzien, etwa dem Methanol oder dem Ethanol aus methoxy- oder ethoxysilanterminierten Prepolymeren.According to the invention, the decimal logarithm of the Po / w value of a blowing agent is used. In the case of propellant gas mixtures, as are usually used, the mean of the log Po / w values of the individual propellant gases of the mixture, weighted with the amount of propellant gas in grams, is calculated and taken as the limiting criterion. It has been shown that the weighted mean of the logarithmic values represents a sufficiently precise approximation. As a result, it was found that in the case of the prepolymers containing silane groups, the non-polarity of the propellant gas component is associated with the polarity of the prepolymer component and / or the agents released from the reactive groups, for example methanol or ethanol from prepolymers terminated with methoxy or ethoxysilane.
Die erfindungsgemäßen Bemessungsregeln gelten sowohl für Einkomponentenschäume als auch für Zweikomponentenschäume. Sie sind ebenfalls anwendbar auf Schäume, die nur teilweise mit einer zweiten, innerhalb eines Druckbehälters ausgelösten Komponente abreagieren und im übrigen mit in der Atmosphäre enthaltenem Wasser, sogenannte 1 ,5-K-Schäume.The design rules according to the invention apply to both one-component and two-component foams. They are also applicable to foams which only partially react with a second component released within a pressure vessel and, moreover, with water contained in the atmosphere, so-called 1.5-component foams.
Es wird angenommen, daß der erfindungsgemäße stabilisierende Effekt der unpolaren bzw. hydrophoben Einstellung der Treibgaskomponente darauf beruht, daß die Treibgase innerhalb der nach dem Ausschäumen gebildeten Zellen besser zurückgehalten werden, weil sie sich nur schlecht in den gegebenenfalls noch zusätzlich mit Methanol oder Ethanol angereicherten polaren Zellmembranen lösen. Durch die Verzögerung des Lösungseffekts hat das Prepolymer Zeit, zu vernetzen, der Alkohol Zeit, abzudampfen und der Schaum Zeit, auszuhärten.It is assumed that the stabilizing effect according to the invention of the non-polar or hydrophobic setting of the propellant gas component is based on the fact that the propellant gases are better retained within the cells formed after foaming because they are poor in the polar, which may also be additionally enriched with methanol or ethanol Loosen cell membranes. By delaying the dissolving effect, the prepolymer has time to cross-link, the alcohol to evaporate and the foam to cure.
Bei den erfindungsgemäßen verwandten Prepolymerkomponenten handelt es sich um solche, wie sie aus dem Stand der Technik bekannt sind. Diese können beispielsweise isocyanatterminiert sein, aber auch silanterminiert, wie beispielsweise aus der WO 00/04069 A1 bekannt. Derartige silanterminierteThe related prepolymer components according to the invention are those as are known from the prior art. These can be, for example, isocyanate-terminated, but also silane-terminated, as is known, for example, from WO 00/04069 A1. Such silane terminated
Prepolymere basieren auf einem üblichen Polyurethangerüst aus einem aromatischen oder aliphatischen Polyisocyanat und einem Polyol, dessen Isocyanat-Gruppen durch Umsetzung mit einer damit reaktiven Silanverbindung umfunktionalisiert wurden. Dafür geeignete Silan-Gruppen sind beispielsweisePrepolymers are based on a conventional polyurethane backbone consisting of an aromatic or aliphatic polyisocyanate and a polyol, the isocyanate groups of which have been functionalized by reaction with a silane compound reactive therewith. Suitable silane groups are, for example
Aminomethoxysilane, insbesondere N-Phenylaminomethyltrimethoxysilan undAminomethoxysilanes, in particular N-phenylaminomethyltrimethoxysilane and
N-Phenylaminomethyldimethoxymethylsilan. Einzelheiten derartigerN-Phenylaminomethyldimethoxymethylsilan. Details of such
Prepolymere sind der WO 00/04069 A1 sowie den WO 02/66532 A1 , WO 02/68491 A1 , WO 02/70586 A1 und WO 02/77072 A1 zu entnehmen, derenPrepolymers can be found in WO 00/04069 A1 and WO 02/66532 A1, WO 02/68491 A1, WO 02/70586 A1 and WO 02/77072 A1, the
Rezepturen hier ausdrücklich einbezogen werden. Der einzuhaltende Mindestwert für den log Po/w, der erfindungsgemäß mit ≥ 1 ,70 angegeben ist, ist im bestimmten Umfang abhängig von der Polarität des Prepolymers bzw. der Polarität des aus dem Prepolymer freigesetzten Produkts der Vernetzungsreaktion und dessen Menge. So ist ein Grenzwert von log Po/w ≥ 1 ,90 in jedem Fall zutreffend für dimethoxymethylsilanterminierte Prepolymere, die bei der Vernetzung nur zwei Moleküle Methanol pro Silaneinheit freisetzen. Bei der Verwendung von trimethoxysilanterminierten Prepolymeren werden drei Moleküle Methanol pro Silan-Gruppe freigesetzt, davon die letzte in einer verzögerten Vernetzungsreaktion nach den beiden ersten. Um der größeren Methanolmenge Rechnung zu tragen, ist hier ein höherer log Po/w-Wert von ≥ 2,35 oder sogar 2,40 angezeigt, um eine hinreichende Schaumqualität zu gewährleisten. Bei Mischsystemen und Systemen, die beispielsweise auf Ethoxysilanen beruhen, sind niedrigere oder Zwischenwerte anwendbar. Die Einhaltung eines log Po/w-Wertes von ≥ 1 ,70 bringt in jedem Fall aber auch bei anderen silanterminierten Prepolymeren Vorteile, beispielsweise solchen, bei denen das Grundgerüst ein anderes als ein Polyurethangerüst ist.Recipes are explicitly included here. The minimum value to be observed for the log Po / w, which according to the invention is ≥ 1.70, depends to a certain extent on the polarity of the prepolymer or the polarity of the product of the crosslinking reaction released from the prepolymer and its amount. A limit value of log Po / w ≥ 1.90 is in any case applicable for dimethoxymethylsilane-terminated prepolymers which release only two molecules of methanol per silane unit when crosslinked. When using trimethoxysilane-terminated prepolymers, three molecules of methanol are released per silane group, the last of which in a delayed crosslinking reaction after the first two. In order to take the larger amount of methanol into account, a higher log Po / w value of ≥ 2.35 or even 2.40 is indicated to ensure sufficient foam quality. In the case of mixing systems and systems based, for example, on ethoxysilanes, lower or intermediate values can be used. Maintaining a log Po / w value of ≥ 1.70 also brings advantages in other cases with other silane-terminated prepolymers, for example those in which the basic structure is different from a polyurethane structure.
Wie schon angemerkt, handelt sich bei den zum Einsatz kommenden Treibgaskomponenten um solche, die unpolar und hydrophob eingestellt sind. Besonders geeignete Treibgase sind Kohlenwasserstoffe mit bis zu 5 C-Atomen, sowohl gesättigte wie auch ungesättigte, sowie Fluorkohlenwasserstoffe, und insbesondere i-Butan, n-Butan, Propan, R227ea (1 ,1 ,1 ,2,3,3,3-Heptafluorpropan), R365mfc (1 ,1 ,1 ,3,3-Pentafluorbutan), R245fa (1 ,1 ,1 ,3,3-Pentafluorpropan), R134a (1 ,1 ,1 ,2-Tetrafluorethan), R152a (1 ,1- Difluorethan) und, eingeschränkt, DME (Dimethylether). Diese Treibgase können allein, in beliebiger Mischung sowie in Abmischung mit anderen treibgasfähigen Verbindungen eingesetzt werden. Im allgemeinen sollte die Treibgaskomponente, je nach Einsatzgebiet und Einsatzbedingungen einen Siedepunkt von ≤ 40 °C und insbesondere ≤ 20 °C aufweisen. In der Regel handelt es sich um verflüssigbare Gase, die in dem Druckbehälter zumindest teilweise, vorzugsweise ganz in der Prepolymerkomponenten gelöst und/oder stabil emulgiert vorliegen. Um die Löslichkeit und Viskosität der Prepolymerzusammensetzung auf für Druckbehälter und die Ausbringung aus Druckbehältem zuträgliche Werte zu bringen, ist es insbesondere bevorzugt, die Zusammensetzung mit üblichen viskositäts- und löslichkeitsbeeinflussenden Zusätzen zu versehen. Die Viskosität kann beispielsweise mit üblichen Phosphaten, die gleichzeitig flammhemmende Wirkung haben, eingestellt werden, etwa mit Triethylphosphat. Zur Regulierung der Viskosität kann ferner in bekannter Weise Vinyltrimethoxysilan eingesetzt werden, das einen positiven Einfluß auf die Löslichkeit der Treibgaskomponente in der Prepolymerkomponente hat. Vinyltrimethoxysilan dient gleichzeitig als Haftvermittler für das Produkt, setzt aber zusätzliche Methanolmengen bei der Reaktion mit Luftfeuchtigkeit frei. Insoweit kann die Polarität der Prepolymerkomponente, ihr Gehalt an freisetzbarem Methanol, ihre Aufnahmefähigkeit/Lösungsvermögen für die Treibgaskomponente und die Polarität des gebildeten Schaums durch den Vinyltnmethoxysilangehalt der Prepolymerzusammensetzung beeinflußt und eingestellt werden.As already noted, the propellant components used are non-polar and hydrophobic. Particularly suitable propellants are hydrocarbons with up to 5 carbon atoms, both saturated and unsaturated, as well as fluorocarbons, and especially i-butane, n-butane, propane, R227ea (1, 1, 1, 2,3,3,3- Heptafluoropropane), R365mfc (1, 1, 1, 3,3-pentafluorobutane), R245fa (1, 1, 1, 3,3-pentafluoropropane), R134a (1, 1, 1, 2-tetrafluoroethane), R152a (1, 1- difluoroethane) and, to a limited extent, DME (dimethyl ether). These propellant gases can be used alone, in any mixture as well as in a mixture with other propellant-capable compounds. In general, the propellant gas component should have a boiling point of ≤ 40 ° C and in particular ≤ 20 ° C, depending on the area of application and conditions of use. As a rule, these are liquefiable gases which are at least partially, preferably completely, dissolved and / or stably emulsified in the pressure vessel in the pressure vessel. In order to bring the solubility and viscosity of the prepolymer composition to values which are conducive to pressure vessels and the output from pressure vessels, it is particularly preferred to provide the composition with customary additives which influence viscosity and solubility. The viscosity can be adjusted, for example, with conventional phosphates, which also have a flame-retardant effect, for example with triethyl phosphate. To regulate the viscosity, vinyltrimethoxysilane can also be used in a known manner, which has a positive influence on the solubility of the propellant gas component in the prepolymer component. Vinyltrimethoxysilane also serves as an adhesion promoter for the product, but releases additional amounts of methanol when reacting with air humidity. In this respect, the polarity of the prepolymer component, its releasable methanol content, its absorption capacity / solvent capacity for the propellant gas component and the polarity of the foam formed can be influenced and adjusted by the vinyltmmethoxysilane content of the prepolymer composition.
Dimethylether kann zur Feinabstimmung der Polarität der Treibgaskomponente eingesetzt werden, da es einen ausgesprochen niedrigen log Po/w-Wert hat. Im allgemeinen ist Dimethylether aber nicht zur Erzielung höherer log Po/w-Werte geeignet.Dimethyl ether can be used to fine-tune the polarity of the propellant gas component because it has an extremely low log Po / w value. In general, however, dimethyl ether is not suitable for achieving higher log Po / w values.
Die Treibgaskomponente macht im allgemeinen 20 bis 40 Volumen-% der erfindungsgemäßen Prepolymerzusammensetzung aus, insbesondere etwa 25 bis 35 Volumen-%. Dabei besteht die Treibgaskomponente zu vorzugsweise wenigstens 2/3 aus unpolaren Bestandteilen, insbesondere wenigstens zu 5/6. Als unpolare Bestandteile werden dabei Bestandteile mit einem log P0/w-Wert von > 1 ,35 angesehen.The propellant gas component generally makes up 20 to 40% by volume of the prepolymer composition according to the invention, in particular approximately 25 to 35% by volume. The propellant gas component preferably consists of at least 2/3 of non-polar components, in particular at least 5/6. Components with a log P 0 / w value of> 1.35 are regarded as non-polar components.
Eine Übersicht über die log Pow-Werte einiger geeigneter Treibgase ist nachstehend wiedergegeben.
Figure imgf000008_0001
An overview of the log Pow values of some suitable propellants is given below.
Figure imgf000008_0001
Im übrigen enthalten die erfindungsgemäßen Prepolymerzusammensetzungen übliche Zusätze und Additive, wie Katalysatoren aus den Herstellungs- und für die Vernetzungsreaktion, Stabilisatoren, Viskositäts- und Rheologieregulatoren, Zellregulatoren, Weichmacher, Flammschutzmittel und dergleichen.In addition, the prepolymer compositions according to the invention contain customary additives, such as catalysts from the preparation and crosslinking reactions, stabilizers, viscosity and rheology regulators, cell regulators, plasticizers, flame retardants and the like.
Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.
Herstellung des PU-Prepolymers:Production of the PU prepolymer:
Das Prepolymer wird erhalten durch Umsetzung von TDI Typ T80 mit einem Polypropylenglykol MG = 400 im molaren Verhältnis NCO : OH = 2,0. Diese Prepolymere werden in üblicher Weise dadurch hergestellt, daß das TDI unter Schutzgas im Reaktor vorgelegt und mit dem Polyol unter Kontrolle der Temperatur so versetzt wird, daß 80 °C nicht überschritten werden. Nach beendeter Polyolzugabe wird noch 3 h bei 80 °C gehalten. Der NCO-Gehalt des fertigen Prepolymers liegt bei theoretischen 11 ,2 % und wird titrimetrisch ermittelt durch die Umsetzung von Prepolymer mit Dibutylamin in toluolischer Lösung und anschießender Rücktitration mit HCI-Lösung. Nach Erreichen eines konstanten NCO-Gehalts wird Vinyltrimethoxysilan zugegen und noch 5 min kräftig gerührt. Zusammensetzung für die Rezepturen:The prepolymer is obtained by reacting TDI type T80 with a polypropylene glycol MG = 400 in a molar ratio of NCO: OH = 2.0. These prepolymers are produced in a conventional manner by introducing the TDI into the reactor under protective gas and adding the polyol while checking the temperature so that 80 ° C. is not exceeded. After the polyol addition has ended, the mixture is kept at 80 ° C. for a further 3 h. The NCO content of the finished prepolymer is theoretical 11.2% and is determined titrimetrically by the reaction of prepolymer with dibutylamine in toluene solution and subsequent back titration with HCl solution. After a constant NCO content has been reached, vinyltrimethoxysilane is added and the mixture is stirred vigorously for a further 5 min. Composition for the recipes:
434 g Desmodur TδO (Bayer AG) 497 g Voranol P400 (DOW) 82 g Vinyltrimethoxysilan434 g Desmodur TδO (Bayer AG) 497 g Voranol P400 (DOW) 82 g vinyl trimethoxysilane
Herstellung des silanterminierten Prepolymers:Preparation of the silane-terminated prepolymer:
Das so erhaltene Prepolymer wird direkt mit den Additiven (Schaumstabilisator, Aminkatalysator), Vinyltrimethoxysilan als Verdünnungsmittel und Haftvermittler) in die Aerosoldose eingewogen. Dann erfolgt die leicht überstoichiometrische Zugabe des Aminosilans, das Verschließen mit einem üblichen Ventil und sofortiges Aufdrücken des Treibgases. Nach beendeter Zugabe wird kräftig geschüttelt. Die Innentemperatur steigt innerhalb von 30 s um 20 bis 30 °C. Die Dosen sind nach einer Nacht Lagerung bei Raumtemperatur gebrauchsfertig.The prepolymer obtained in this way is weighed directly into the aerosol can with the additives (foam stabilizer, amine catalyst), vinyltrimethoxysilane as diluent and adhesion promoter. Then the slightly over-stoichiometric addition of the aminosilane takes place, the closure with a conventional valve and immediate injection of the propellant gas. When the addition is complete, shake vigorously. The internal temperature rises by 20 to 30 ° C within 30 s. The cans are ready for use after overnight storage at room temperature.
Zur Reaktionskontrolle wird der Doseninhalt FT-IR-spektroskopisch untersucht. Es ist kein Isocyanatpeak mehr nachweisbar.To check the reaction, the contents of the can are examined by FT-IR spectroscopy. An isocyanate peak is no longer detectable.
Prepolymer 1 : Umsetzungsprodukt von PU-Prepolymer mitPrepolymer 1: reaction product of PU prepolymer with
N-Phenylaminomethyltrimethoxysilan.N-phenylaminomethyltrimethoxysilane.
Prepolymer 2: Umsetzungsprodukt von PU-Prepolymer mitPrepolymer 2: reaction product of PU prepolymer with
N-Phenylaminomethyldimethoxymethylsilan.N-Phenylaminomethyldimethoxymethylsilan.
Rezepturenrecipes
Unter Verwendung der vorstehend beschriebenen silanterminierten Prepolymere wurden die in der nachstehenden Tabelle aufgeführten Prepolymerzusammensetzungen mit den angegebenen Treibgaskomponenten hergestellt und aus einer herkömmlichen Druckdose verschäumt. Der verwandte Stabilisator ist ein Schaumstabilisator der Firma Goldschmidt AG in Essen, der Katalysator ZF-20 Bis-(2-dimethylaminoethyl)ether der Firma Huntsman. Zur Auswertung wurden zwei Spanplatten mit den Abmessungen 14 x 14 x 1 ,9 cm 20 s in Wasser eingetaucht. Dann wurden die Platten 100 s senkrecht aufgestellt, um das Wasser ablaufen zu lassen und stehende Nässe zu vermeiden. Mit Fugenabstandshaltern (Stäben aus Polyethylen) wurde eine liegende Fuge der Dimension 14 x 9,5 x 2,5 cm dargestellt. Die Fuge wurde mit einem Gewicht von 12,5 kg beschwert und vollständig ausgeschäumt. Nach einem Tag wurde der herausgequollene Schaum abgeschnitten und die Schaumqualität in der Fuge beurteilt. Dazu wurde die Fuge längs durchgeschnitten. Zur Bewertung wurden die Werte 1 (homogen durchgehärtete Schaumfuge), 2 (Rißbildung in der Schaumfuge) und 3 (kompletter Kollaps in der Fuge) vergeben. Die Ergebnisse sind ebenfalls in der nachstehenden Tabelle wiedergegeben. Using the silane-terminated prepolymers described above, the prepolymer compositions listed in the table below were prepared with the propellant components indicated and were foamed from a conventional pressure can. The related stabilizer is a foam stabilizer from Goldschmidt AG in Essen, the catalyst ZF-20 bis (2-dimethylaminoethyl) ether from Huntsman. For evaluation, two particle boards with the dimensions 14 x 14 x 1.9 cm were immersed in water for 20 s. Then the plates were set up vertically for 100 s in order to allow the water to run off and to avoid standing moisture. A horizontal joint measuring 14 x 9.5 x 2.5 cm was shown with joint spacers (rods made of polyethylene). The joint was weighted with a weight of 12.5 kg and completely foamed. After a day, the swollen foam was cut off and the foam quality in the joint was assessed. For this, the joint was cut lengthways. The values 1 (homogeneously hardened foam joint), 2 (crack formation in the foam joint) and 3 (complete collapse in the joint) were assigned for evaluation. The results are also shown in the table below.
Rezepturenrecipes
Figure imgf000011_0001
Figure imgf000011_0001
Alle Angaben in Gewichtsteilen, soweit nicht anders angegeben. All parts in parts by weight unless otherwise stated.

Claims

Patentansprüche claims
1. Prepolymerzusammensetzung, insbesondere für die Erzeugung von Dämmschäumen aus Druckbehältern, mit einer Prepolymerkomponenten, die ein Prepolymer mit Silan-Gruppen zur Vernetzung des Prepolymers mit einer zweiten Komponenten aufweist sowie übliche Zusätze, und einer Treibgaskomponenten, die unter dem im Druckbehälter herrschenden Druck flüssig ist und zumindest teilweise in der Prepolymerkomponenten gelöst vorliegt, d a d u r c h g e k e n n z e i c h n e t , daß die Treibgaskomponente einen Wert von log P0/w ≥ 1 ,70 aufweist, wobei Po/w für den Verteilungskoeffizienten der Treibgaskomponente in Oktanol/Wasser steht.1. prepolymer composition, in particular for the production of insulating foams from pressure vessels, with a prepolymer component which has a prepolymer with silane groups for crosslinking the prepolymer with a second component, as well as conventional additives, and a propellant gas component which is liquid under the pressure prevailing in the pressure vessel and is at least partially dissolved in the prepolymer component, characterized in that the propellant gas component has a value of log P 0 / w ≥ 1.70, where Po / w stands for the distribution coefficient of the propellant gas component in octanol / water.
2. Prepolymerzusammensetzung nach Anspruch 1 , dadurch gekennzeichnet, daß das Prepolymer Methyldimethoxysilan-Gruppen aufweist.2. Prepolymer composition according to claim 1, characterized in that the prepolymer has methyldimethoxysilane groups.
3. Prepolymerkomponente nach Anspruch 2, dadurch gekennzeichnet, daß Wert log Pow der Treibgaskomponente > 1 ,90.3. prepolymer component according to claim 2, characterized in that value log Pow of the propellant gas component> 1, 90th
4. Prepolymerzusammensetzung nach Anspruch 1 , dadurch gekennzeichnet, daß das Prepolymer Trimethoxysilan-Gruppen aufweist.4. Prepolymer composition according to claim 1, characterized in that the prepolymer has trimethoxysilane groups.
5. Prepolymerzusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß der Wert log Pow der Treibgaskomponente > 2,35 ist. 5. prepolymer composition according to claim 4, characterized in that the value log Pow of the propellant gas component is> 2.35.
6. Prepolymerzusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Treibgaskomponente einen Siedepunkt von < 40 °C hat.6. Prepolymer composition according to one of the preceding claims, characterized in that the propellant gas component has a boiling point of <40 ° C.
7. Prepolymerzusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Treibgaskomponente einen7. prepolymer composition according to one of the preceding claims, characterized in that the propellant gas component
Siedepunkt von < 20 °C hat.Has a boiling point of <20 ° C.
8. Prepolymerzusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Treibgaskomponente i-Butan, n-Butan, Propan, R227ea, R365mffc, R245fa, R134a, R152a, Dimethylether oder Mischungen derselben untereinander oder mit weiteren Treibgasen enthält.8. Prepolymer composition according to one of the preceding claims, characterized in that the propellant gas component contains i-butane, n-butane, propane, R227ea, R365mffc, R245fa, R134a, R152a, dimethyl ether or mixtures thereof with one another or with further propellant gases.
9. Prepolymerzusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Treibgaskomponente 20 bis 40 Volumen-% der Prepolymerzusammensetzung ausmacht.9. prepolymer composition according to one of the preceding claims, characterized in that the propellant gas component makes up 20 to 40% by volume of the prepolymer composition.
10. Prepolymerzusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Treibgaskomponente zu wenigstens 2/3 aus unpolaren Treibmitteln besteht.10. Prepolymer composition according to one of the preceding claims, characterized in that at least 2/3 of the propellant gas component consists of non-polar propellants.
11. Prepolymerzusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Treibgaskomponente zu wenigstens 5/6 aus unpolaren Bestandteilen besteht.11. Prepolymer composition according to one of the preceding claims, characterized in that at least 5/6 of the propellant gas component consists of non-polar constituents.
12. Verwendung einer Treibgasmischung mit einem Wert log Po/w von12. Use of a propellant gas mixture with a log Po / w value of
> 1 ,70 zur Erzeugung von Dämmschäumen aus Silan-Gruppen enthaltenden Prepolymeren in Druckbehältern.> 1, 70 for the production of insulation foams from prepolymers containing silane groups in pressure vessels.
13. Verwendung nach Anspruch 12, dadurch gekennzeichnet, daß das Prepolymer ein silanterminiertes Prepolymer ist.13. Use according to claim 12, characterized in that the prepolymer is a silane-terminated prepolymer.
14. Verwendung nach Anspruch 13, dadurch gekennzeichnet, daß das14. Use according to claim 13, characterized in that the
Prepolymer Trimethoxysilan-Gruppen enthält. Contains prepolymer trimethoxysilane groups.
15. Verwendung nach Anspruch 14, dadurch gekennzeichnet, daß die Treibgaskomponente einen Wert log Po/w von > 2,35 aufweist.15. Use according to claim 14, characterized in that the propellant gas component has a log Po / w value of> 2.35.
16. Verwendung nach einem der Ansprüche 12 bis 15, dadurch gekennzeichnet, daß die Treibgaskomponente i-Butan, n-Butan, Propan, s R227ea, R365mffc, R245fa, R143a, R152a, Dimethylether oder Mischungen derselben untereinander oder mit weiteren Treibgasen enthält. 16. Use according to one of claims 12 to 15, characterized in that the propellant gas component contains i-butane, n-butane, propane, s R227ea, R365mffc, R245fa, R143a, R152a, dimethyl ether or mixtures thereof with one another or with further propellant gases.
PCT/EP2003/014765 2003-01-23 2003-12-23 Hydrophobic propellant gas mixtures for producing insulating foams WO2004065448A1 (en)

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EP03815373A EP1585778B1 (en) 2003-01-23 2003-12-23 Hydrophobic propellant gas mixtures for producing insulating foams
DE50313106T DE50313106D1 (en) 2003-01-23 2003-12-23 HYDROPHOBIC FLUID MIXTURES FOR THE PRODUCTION OF INSULATED FOAM
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